Exciton, singlet dissociation

The interpretation of our CPG data is complicated by the presence of comparatively fast radiative and nonradiative decay channels for the singlet exciton, which compete with the field-induced dissociation. In order to provide a clear picture of the observed mechanism and disentangle it from the singlet exciton decay dynamics, we define the following phenomenological time-dependent parameter ... 

If E is greater than the electron affinity E of the accepter, then the photoinduced forward electron-transfer reaction will be exothermic. This approach can be used to determine the E for both singlet and triplet excitons from the corresponding singlet and triplet state oo values. A similar calculation of an acceptor exciton s electron affinity ( ) may be made, to assess whether acceptor exciton-dissociation... 

Although a signal was detected also in irradiated pyrimidine solutions under similar conditions, it was attributed to dissociation products of the pyrimidine molecule and not to photoionization. If the purine solutions contained ethanol, then the signal of the CH3CHOH radical could also be detected this did not happen in ethanolic pyrimidine solutions. The possible importance of photoionization as the primary process in the photochemistry of nucleic acid derivatives has been supported by Kearns, from a study of photoionization in anthracene single crystals.115 He concluded that anthracene photoionization occurred via the interaction of two singlet excitons. 

A theoretical study by the same author suggests that RDX forms charge transfer complexes upon crystn which are unique because their charge transfer exciton band is of lower energy than the singlet exciton band of their molecular crysts. Static reactivity indices were used to predict the likely primary dissociative products obtainable from each excited state of secondary nitramines theory predicts that the axial and equatorial nitramine groups of the polynitra-mines RDX, alpha- and beta-HMX, may possess quite novel selective decompn paths and hence give different primary dissociative products... 

Photoexcitation of the complex is accompanied by charge transfer from the donor TBPDA molecule to the acceptor C6o one and CT-exciton is formed. Depending on mutual orientation of spins of components (electrons and holes), CT-exciton can be either a singlet or a triplet one. Free charge carriers are formed in molecular crystals mainly due to thermal or impurity dissociation of triplet CT-excitons [6],... 

Okamoto et al. (1973,1973a, 1973b) measured photogeneration efficiencies of PVK. The results were explained by the field-assisted thermal dissociation of an exciplex formed between an excited carbazole group and an acceptor impurity. Okamoto et al. (1975) measured the efficiencies of /3-N-caibazolyl-ethyl vinyl ether, an oligomer of N-vinylcaibazole, and PVK. The efficiencies of the three compounds were comparable. The results were described by the dissociation of singlet excitons. 

Harima et al. (1989) measured the photogeneration efficiencies of 5,10,15,20-tetraphenylporphyrin (TPP) and its Zn complex (ZnTPP) doped with tetracyano-quinodimethane (TCNQ), o-chloranil (Chi), phenothiazine (Pz), and I. TCNQ, Chi, and I are electron acceptors while Pz is a donor. The porphyrins were selected on the basis of differences in exciton diffusion lengths (Tanimura et al., 1980 Yamashita et al., 1987) and oxidation potentials (Felton, 1978). The photogeneration of I doped ZnTPP was described by a direct ionization process via a singlet state of ZnTPP and ascribed to a reduction of the electron-hole recombination rate in the depletion layer. For TPP doped with Chi, Pz, or I, the results were explained by exciplex dissociation (Loutfy and Menzel, 1980). For... 

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